Based from Sears and Zemansky’s University Physics

with Modern Physics 13th ed

Review question
E0. At what temperature (in Celsius scale) would one mole of molecular
oxygen (O2) have 5.00 x 103 J of translational kinetic energy?
3
𝐾𝑡𝑟 = 𝑛𝑅𝑇
2
Since the problem is only asking for
3
translational kinetic energy, Cv = . If the
2
5
question is TOTAL KE, then Cv = since a
2
molecule of O2 is diatomic.
3
5,000 = (1.00)(8.314)𝑇
2

𝑇 = 400 𝐾 = 127.8∘ 𝐶
Thermodynamic Systems
• Thermodynamic system is a collection of objects which may exchange
energy with its environment.
• A thermodynamic process causes change in the state (𝑝, 𝑉, 𝑇, 𝑛) of a
thermodynamic system.
– The thermodynamic processes are:
1. Isobaric process – pressure (p) is kept constant
2. Isothermal process – temperature (T) is constant
3. Isochoric process – volume (V) is constant
4. Adiabatic process – no heat (Q) exchange in and out of the system
Heat and Work Sign Convention

• W (+) – work done by the system;

corresponds to energy leaving the
system
• W (-) – work done on the system;
corresponds to energy entering the
system
• Q (+) – heat flow into the system Heat Work
• Q (-) – heat flow out of the system
Heat and Work Sign Convention

• Work done by the system is

positive
• The piston moves in the same
direction where the molecule
pushes it.
• This results into loss of kinetic
energy.
Heat and Work Sign Convention

• Work done by the system is

negative
• The piston moves in opposite
direction where the molecule
pushes it.
• This results into an increase of
kinetic energy.
Work Done during Volume Changes

Isobaric process
If the pressure is kept constant, then
𝑊 = 𝑝 (𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 )

Isothermal process
For constant temperature, expansion or contraction
of an ideal gas:
𝑑𝑊 = 𝑝𝐴 𝑑𝑥 𝑉𝑓𝑖𝑛𝑎𝑙
𝑛𝑅𝑇
= 𝑝 𝑑𝑉 𝑊=න 𝑝 𝑑𝑉 𝑝 𝑉 = 𝑛𝑅𝑇 𝑝 =
𝑉𝑓𝑖𝑛𝑎𝑙 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑉
𝑊=න 𝑝 𝑑𝑉 𝑉𝑓𝑖𝑛𝑎𝑙
𝑛𝑅𝑇
𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑊=න 𝑑𝑉 = 𝑛𝑅𝑇(𝑙𝑛𝑉𝑓 − 𝑙𝑛𝑉𝑖 )
𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑉
This is the general formula for work
but changes according to the 𝑉𝑓
𝑊 = 𝑛𝑅𝑇𝑙𝑛( )
thermodynamic process. 𝑉𝑖
pV Diagrams

Isobaric process + Work -- Work

(Constant Pressure) Isothermal process
(Constant Temperature)
Isothermal Process
For an isobaric (constant pressure) expansion or contraction of an ideal gas:
𝑊 = 𝑝 (𝑉𝑓𝑖𝑛𝑎𝑙 − 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 )
Work done by n moles of ideal gas undergoing an isobaric expansion and its volume
changes from V1 to V2.
Example
Two moles of an ideal gas are heated at constant pressure from 𝑇 = 27∘ C to 𝑇 = 107∘ C.
(a) Draw a pV-diagram for this process, label the initial state with i and the final state
with f. Indicate also the direction of the process.
(b) Calculate the work done by the gas
(a) (b) 𝑝𝑖 𝑉𝑖 = 𝑛𝑅𝑇𝑖 and 𝑝𝑓 𝑉𝑓 = 𝑛𝑅𝑇𝑓 but 𝑝𝑖 = 𝑝𝑓 = 𝑝
𝑝
𝑖 𝑓 𝑝𝑉𝑖 = 𝑛𝑅𝑇𝑖 𝑝𝑉𝑓 = 𝑛𝑅𝑇𝑓
𝑊 = 𝑝 (𝑉𝑓 − 𝑉𝑖 ) 𝑊 = 𝑛𝑅(𝑇𝑓 −𝑇𝑖 )
𝐽
= 𝑝𝑉𝑓 − 𝑝𝑉𝑖 𝑊 = 2 (8.314 )(380𝐾 − 300𝐾)
𝑚𝑜𝑙 ∙ 𝐾
𝑉 = 𝑛𝑅𝑇𝑓 − 𝑛𝑅𝑇𝑖 𝑊 =1,330 J
Isothermal Process
For an isothermal (constant temperature) expansion or contraction of an ideal
gas: 𝑉2
𝑊 = 𝑛𝑅𝑇 ln
𝑉1
Work done by n moles of ideal gas undergoing an isothermal expansion at
temperature T and its volume changes from V1 to V2.

Example (a) 𝑝1 𝑉1 = 𝑝2 𝑉2
𝑝 𝑃1
Two moles of an ideal gas are 𝑓 𝑊 = 𝑛𝑅𝑇 ln
compressed in a cylinder at 3𝑝0 𝑃2
constant temperature at 65.0°C 𝑃0
until the original pressure has tripled. 𝑖 𝑊 = 𝑛𝑅𝑇 ln
𝑝0 3𝑃0
(a) Sketch a pV-diagram for this 1
process. 𝑉 𝑊 = 𝑛𝑅𝑇 ln( )
(b) 3
(b) Calculate the amount of work 𝑉2
𝑊 = 𝑛𝑅𝑇 ln 𝑊 = −6180 J
done. 𝑉1
Isothermal Process
Example
In an isothermal compression of n moles of an ideal gas at temperature T,
how many times larger than the initial volume must the final volume be if the
work done on the gas is 3nRT?
𝑉𝑓
𝑊 = −3𝑛𝑅𝑇 −3𝑛𝑅𝑇 = 𝑛𝑅𝑇 ln
𝑉𝑖
work done on the gas so W is negative
𝑉𝑓
𝑉𝑓 −3 = ln
𝑊 = 𝑛𝑅𝑇 ln 𝑉𝑖
𝑉𝑖 𝑉𝑓
−3
𝑒 =
work done in an isothermal compression 𝑉𝑖
𝑉𝑓 = 𝑒 −3 𝑉𝑖
Work Done In A Thermodynamic Process
Work done by the system depends not only on the initial and final states,
but also on the intermediate states
Heat Added in a Thermodynamic Process

• It is not enough to know the initial and final state to determine if heat is
added or removed in a thermodynamic system.
• Heat added or removed depends on the actual thermodynamic paths
and not only the initial and final state.
Internal Energy
• We can think of this as the sum of the kinetic energies of all the
constituent particles of a system, plus the sum of all the potential energies
of interactions among these particles
• We are interested in the change in the internal energy (U)

• When no work is done and heat enters the system

• When no heat enters and work is done by the system

The First Law of Thermodynamics
States that in general,

• The change in internal energy is path-independent and only depends on

the initial and final states
It implies that energy, which includes
heat, is conserved; that is, one form
of energy can be converted into
another, but energy can neither be
created nor destroyed.

It means that the total amount of

energy in the universe is a constant.
The First Law of Thermodynamics
Conservation of Energy
• One of the first to state the law of energy conservation was the German
physician Robert Mayer (1814–1878).

• In 1840 Mayer was the physician on the schooner Java, which sailed for the
East Indies. While aboard the ship, he read a treatise by the French scientist
Laurent Lavoisier.
Treatise by the French scientist Laurent Lavoisier
➢ the heat produced by animals is due to the slow combustion of food in
their bodies
➢ less food is burned by the body in a hot environment than in a cold
one

• When the ship reached the tropics, many of its crew became sick with fever.

• Applying the usual remedy for fever, Mayer bled his patients.
The First Law of Thermodynamics
• He noticed that the venous blood, which is normally dark red, was nearly as red as
arterial blood.
• This was considered as a verification of Lavoisier’s suggestion.
• Because in the tropics less fuel is burned in the body, the oxygen content of
the venal blood is high, giving it the brighter color.

• Mayer suggested that in the body there is an exact balance of energy (which he
called force).
• The energy released by the food is balanced by the lost body heat and the work
done by the body.

• Mayer wrote in an article published in 1842, “Once in existence, force [energy] cannot
be annihilated—it can only change its form.”

• More evidence had to be presented before conservation of energy was accepted as

a law, but it is interesting that such a fundamental physical law was first suggested from
the observation of human physiology.
 The First Law of Thermodynamics
➢ Conservation of energy is implicit in all calculations of energy balance in living
systems.

➢ The body of an animal contains internal thermal energy 𝐸𝑡 , which is the product of
the mass and specific heat, and chemical energy 𝐸𝑐 stored in the tissue of the body.

➢ In terms of energy, the activities of an animal

consist of simply eating, working, and rejecting
excess heat by means of various cooling mechanisms
(radiation, convection, etc.).

➢ The first law allows us to draw some conclusions about the energetics of the animal.

➢ For example, if the internal temperature and the weight of the animal are to remain
constant (i.e., 𝐸𝑐 and 𝐸𝑡 constant), over a given period of time the energy intake
must be exactly equal to the sum of the work done and the heat lost by the body.

➢ An imbalance between intake and output energy implies a change in the sum 𝐸𝑐 +
𝐸𝑡 .
The First Law and the Thermodynamic Processes

Adiabatic
– No heat transfer into or out of a system, Q = 0

– In many (but not all) systems, an increase of internal energy is

accompanied by a rise in temperature and a decrease in internal
energy by a drop in temperature
– Example: system is insulated; process is carried out so quickly
The First Law and the Thermodynamic Processes

Isochoric
– Constant-volume process, W = 0

– All the energy added as heat remains in the system as an increase in

internal energy
– Example: heating a gas in a non-insulated, closed constant-volume
container
– Does work always involve a change in volume?
The First Law and the Thermodynamic Processes
Isobaric
– Constant-pressure process
– In general, none of the quantities ΔU, Q and W are zero but W is
computed easily

– Example: boiling water at constant pressure

Example Δ𝑈 = 𝑄 − 𝑊
A gas in a cylinder expands from a volume of = 1.15 × 105 − 𝑊
0.110 m3 to 0.320 m3. Heat flows into the gas just
rapidly enough to keep the pressure constant at = 8.04 × 104 J
1.65 x 105 Pa. The total heat added is 1.15 x 105 J. Ideal gas equation is not used in
any of our calculations. So it
(a) E1. Find the work done by the gas.
does not matter.
(b) Find the change in internal energy of the gas.
The 1st law of thermodynamics is
(c) Does it matter whether the gas is ideal?
applicable even to non ideal
gas.
The First Law and the Thermodynamic Processes

Isothermal
– Constant-temperature process
– In general, none of the quantities ΔU, Q and W are zero
– Any heat flow in or out of the system must occur slowly enough so that
thermal equilibrium is maintained
– Example: expansion of an ideal gas maintained at constant
temperature
Cyclic Process
• A process that eventually returns a system to its initial state
• Here, the final internal energy is equal to the initial internal energy so that

Isolated Systems
• System does no work on its surroundings and has no heat flow to or from
its surroundings

• Different from a “closed” system where only matter is not allowed to enter
or leave the system
Adiabatic Process for an Ideal Gas
Adiabatic (Q = 0)
Where Cv= molar heat
𝑑𝑈 = −𝑑𝑊 capacity at constant V
𝑛𝐶𝑉 𝑑𝑇 = −𝑝𝑑𝑉
𝑛𝑅𝑇
𝑛𝐶𝑉 𝑑𝑇 = − 𝑑𝑉
𝑉
𝑑𝑇 𝑅 𝑑𝑉 𝑑𝑇 𝑑𝑉
=− =− 𝛾−1
𝑇 𝐶𝑉 𝑉 𝑇 𝑉

Interpretation
• An adiabatic expansion (dV > 0)
causes a drop in temperature (dT < 0)
• An adiabatic compression (dV < 0)
causes a rise in temperature (dT > 0)
Adiabatic Ideal Gas
• Work done

– When temperature decreases (T1 > T2), then gas does work (W > 0)
– When temperature increases (T1 < T2), then work is done on the gas (W
< 0)

Where Cv= molar heat capacity at constant V

Cp= molar heat capacity at constant pressure
Work done by an ideal gas for different processes
Isobaric

Isochoric

Isothermal

Adiabatic